Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4866—Polyethers having a low unsaturation value
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/088—Removal of water or carbon dioxide from the reaction mixture or reaction components
  • C08G18/0885—Removal of water or carbon dioxide from the reaction mixture or reaction components using additives, e.g. absorbing agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/2805—Compounds having only one group containing active hydrogen
  • C08G18/2815—Monohydroxy compounds
  • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/2805—Compounds having only one group containing active hydrogen
  • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
  • C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4825—Polyethers containing two hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2190/00—Compositions for sealing or packing joints

Definitions

• the present invention relates to a process for preparing moisture-curable urethanes containing reactive silane groups from polyether polyols having a low degree of unsaturation and to the use of these polyurethanes as sealants, adhesives and coatings.
• silane-terminated polyurethanes Polyether urethanes containing reactive silane groups, also referred to as silane-terminated polyurethanes (STPs), and their use as sealants and adhesives are known and described, e.g., in U.S. Pat. Nos. 5,554,709; 4,857,623; 5,227,434 and 6,197,912; and WO 02/06367.
• the silane-terminated polyurethanes may be prepared by various methods. In one method the silane-terminated polyurethanes are prepared by reacting diisocyanates with polyether polyols to form isocyanate-terminated prepolymers, which are then reacted with aminosilanes to form the silane-terminated polyurethanes.
• the sealants may also be prepared by reacting unsaturated monools with diisocyanates to form intermediates containing unsaturated end groups and then converting these unsaturated groups to alkoxysilane groups by hydrosilylation.
• the sealants are prepared in one step by the reaction of polyether diols with isocyanatosilanes
• the sitane-terminated polyurethanes should have a number average molecular weight of 6000 to 20,000.
• One method of obtaining this molecular weight is to use polyether diols prepared by the KOH process and having a molecular weight of 2000 to prepare the isocyanate-terminated prepolymers.
• the presence of urethane groups causes the products to have a high viscosity.
• the high viscosity is reduced by the addition of higher amounts of plasticizer and lesser amounts of fillers, resulting in more expensive sealant products.
• Another method of obtaining high molecular weight sealants is by using high molecular weight polyether diols having a low degree of unsaturation and prepared using special catalysts as described in EP-A 0,546,310, EP-A 0,372,561 and DE-A 19,908,562.
• these polyether diols are used, the resulting sealants have excellent tensile strength, but the sealants are too brittle for many applications because the elongation is too low and the 100% modulus is too high.
• WO 00/26271 discloses the preparation of silane-terminated polyether urethanes from polyether polyols having a low degree of unsaturation and aspartate-functional silanes.
• the products are prepared by reacting diisocyanates with high molecular weight polyether diols to form NCO prepolymers, which are then capped with aspartate-functional silanes to form silane-terminated polyether urethanes.
• This application does not disclose mixtures of disilane-terminated polyether urethanes with polyether urethanes containing one reactive silane group.
• U.S. Pat. No. 6,265,517 describes a similar process for preparing silane-terminated polyether urethanes from polyether polyols having a low degree of unsaturation and aspartate-functional silanes.
• the patent requires the starting polyol to have a monool content of less than 31 mole %, and teaches that a relatively high monool content is highly undesirable because monools react with isocyanates thereby reducing crosslinking and curing of the prepolymer.
• the patent also requires the aspartate silanes to be prepared from dialkyl maleates in which the alkyl groups each contain more than four carbon atoms.
• EP 0,372,561 discloses polyether urethanes containing reactive silane groups and prepared from polyether polyols having a low degree of unsaturation.
• polyether urethanes containing one reactive silane group are disclosed. This application fails to disclose the use of aspartate-functional silanes to incorporate the reactive silane groups.
• the polyether urethane component containing two or more reactive silane groups are prepared from high molecular weight polyether polyols having a low degree of unsaturation.
• at least a portion of the reactive silane groups present in at least one of the two components are incorporated by the use of silanes containing secondary amino groups.
• the polyether urethane components described in the copending applications are prepared separately and subsequently blended to form the moisture-curable polyether urethanes according to the invention.
• This object may be achieved with process of the present invention in which the moisture-curable polyether urethanes containing a mixture of polyether urethane component having two or more reactive silane groups and a polyether urethane component having one reactive silane group are prepared simultaneously instead of being prepared separately and mixed.
• polyether urethanes obtained according to the process of present invention possess the same properties as the products obtained in accordance with the copending applications because a greater variety of by-products are obtained according to the present invention and it could not be predicted that the presence of these by-products would not affect the valuable properties of the moisture-curable polyurethanes.
• the present invention relates to a process for preparing a moisture-curable, alkoxysilane-functional polyether urethane by reacting at an NCO:OH equivalent ratio of 1.5:1 to 2.5:1
• component a 20 to 100% by weight, based on the weight of component a), of a polyether containing two hydroxyl groups and one or more polyether segments, wherein the polyether segments have a number average molecular weight of at least 3000 and a degree of unsaturation of less than 0.04 milliequivalents/g, provided that the sum of the number average molecular weights of all of the polyether segments per molecule averages 6000 to 20,000, and
• component a 0 to 80% by weight, based on the weight of component a), of a polyether containing one hydroxyl group and one or more polyether segments having a number average molecular weight of 1000 to 15,000, with
• component b 0 to 80% by weight, based on the weight of component b), of a compound containing one isocyanate group
• component c) a compound containing an isocyanate-reactive group and one more reactive silane groups in which at least 10 mole % of component c) is a compound corresponding to the formula
• X represents identical or different organic groups which are inert to isocyanate groups below 100° C., provided that at least two of these groups are alkoxy or acyloxy groups,
• Y represents a linear or branched alkylene group containing 1 to 8 carbon atoms
• R 1 represents an organic group which is inert to isocyanate groups at a temperature of 100° C. or a group corresponding to formula II
• reactive silane group means a silane group containing at least two alkoxy or acyloxy groups as defined by substituent “X”.
• a silane group containing two or three alkoxy and/or acyloxy groups is considered to be one reactive silane group.
• a urethane is a compound containing one or more urethane and/or urea groups. These compounds preferably contain one or more urethane groups and may optionally contain urea groups. More preferably, these compounds contain both urethane and urea groups.
• the isocyanate-containing reaction products used for preparing the moisture-curable polyether urethanes may be prepared by several methods. For example, they may be prepared by reacting a mixture of polyether diol a-i) and polyether monool a-ii) with an excess of diisocyanate b-i), to form an isocyanate-containing reaction product containing NCO prepolymers and monoisocyanates formed by the reaction of one mole of a diisocyanate with one mole of a polyether monool.
• polyether monool a-ii) is present in an amount of at least 10% by weight, based on the weight of component a).
• the isocyanate-containing reaction products are prepared by reacting polyether diol a-i) with an excess of diisocyanate b-i) and monoisocyanate b-ii) to form an isocyanate-containing reaction product containing NCO prepolymers and monoisocyanates formed by the reaction of one mole of a monoisocyanate with one mole of a polyether diol.
• monoisocyanate b-ii) is present in an amount of at least 10% by weight, based on the weight of component b).
• the isocyanate-containing reaction products are prepared by reacting the isocyanate component with the polyether component at an NCO:OH equivalent ratio of a 1.5:1 to 2.5:1, preferably 1.8:1 to 2.2:1 and more preferably 1.9:1 to 2.1:1 and most preferably 2:1. It is especially preferred to react one mole of the isocyanate component for each equivalent of hydroxyl groups.
• the reaction mixture contains the 2/1 adduct of the diisocyanate and diol; minor amounts of higher molecular weight oligomers, such as the 3/2 adduct; a monoisocyanate, which is the 1/1 adduct of the monool and diisocyanate; non-functional polymers, which are formed by the reaction of two molecules of the monool with one molecule of the diisocyanate; various products containing both diols and monools; and a minor amount of unreacted diisocyanate, which can be removed, e.g., by distillation, or which can remain in the reaction mixture.
• the isocyanate-containing reaction products are reacted with compounds c) containing reactive silane groups at equivalent ratio of isocyanate groups to isocyanate-reactive groups of 0.8:1 to 1.1:1, preferably 0.9:1 to 1.05:1 and more preferably about 1:1.
• the moisture-curable polyether urethanes may also be prepared by reacting an excess of diisocyanates b) with aminosilanes c) to form a monoisocyanate and then reacting the resulting monoisocyanate with a mixture of polyethers a-i) and a-ii) to form the polyether urethanes.
• the moisture-curable, polyether urethanes obtained according to the process of the present invention contain polyether urethanes A), which contain two or more, preferably two, reactive silane groups, and polyether urethanes B), which contain one reactive silane group. Also present are polymers C), which are the reaction products of unreacted isocyanates b) with aminosilanes c). Polymers C) are preferably present in an amount of less then 5% by weight.
• the reaction mixture also contains non-functional polymers D), which are formed by the reaction of two molecules of the monool with one molecule of the diisocyanate, two molecules of the monoisocyanate with one molecule of the diol, or one molecule of the monool with one molecule of a monoisocyanate.
• Non-functional polymers D) are generally present in an amount of less than 30% by weight.
• NCO:OH equivalent ratio it is also possible to adjust the NCO:OH equivalent ratio to form additional amounts of non-functional polymers D) are formed from the reactants as previously described. These polymers remain in the reaction mixture and function as plasticizers during the subsequent use of the moisture-curable, polyether urethanes according to the invention.
• Suitable polyethers for use as component a-i) include polyethers containing two hydroxyl groups and optionally up to 20% by weight, based on the weight of component a-i), of polyethers containing more than 2 hydroxyl groups.
• the polyethers contain one or more, in some cases one, polyether segment.
• the polyether segments have a number average molecular weight of at least 3000, in some cases at least 6000 and in other cases at least 8000.
• the number average molecular weight of the poly ether segment can be up to 20,000, in some cases up to 15,000 and in other cases up to 12,000.
• the number average molecular weight of the polyether segments can vary and range between any of the values recited above.
• polyether segments when the polyether segments have a number average molecular weight of 3000, then two or more of these segments must be present to provide that the number average molecular weights of all of the polyether segments per molecule averages between 6000 to 20,000.
• the polyethers have a maximum total degree of unsaturation of less than 0.04 milliequivalents/g (meq/g) in some cases less than 0.02 meq/g, in other cases less than 0.01 meq/g and in some situations 0.007 meq/g or less.
• the amount of unsaturation will vary depending on the method used to prepare the polyether as well as the molecular weight of the polyerther.
• Such polyether diols are known and can be produced by, as a non-limiting example, the propoxylation of suitable starter molecules.
• minor amounts (up to 20% by weight, based on the weight of the polyol) of ethylene oxide can be used.
• ethylene oxide it can be used as the initiator for or to cap polypropylene oxide groups.
• suitable starter molecules include diols such as ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6 hexanediol and 2-ethylhexanediol-1,3. Also suitable are polyethylene glycols and polypropylene glycols.
• Suitable methods for preparing polyether polyols are known and are described, for example, in EP-A 283 148; U.S. Pat. Nos. 3,278,457; 3,42,256; 3,829,505; 4,472,560; 3,278,458; 3,427,334; 3,941,849; 4,721,818; 3,278,459; 3,427,335 and 4,355,188. They are preferably prepared using double metal cyanides as catalysts.
• polyether polyols In addition to the polyether polyols, minor amounts (up to 20% by weight, based on the weight of the polyol) of low molecular weight dihydric and trihydric alcohols having a molecular weight 32 to 500 can also be used. Suitable examples include ethylene glycol, 1,3-butandiol, 1,4-butandiol, 1,6-hexandiol, glycerine or trimethylolpropane. However, the use of low molecular weight alcohols is less preferred.
• Polyethers a-i) are present in a amount of up to 100% by weight.
• polyether monools a-ii) are used as the sole monofunctional component, polyethers a-i) are present in a minimum amount of 20% by weight, preferably 30% by weight and more preferably 40% by weight, and a maximum amount of 90% by weight, preferably 80% by weight and more preferably 70% by weight.
• the preceding percentages are based on the total weight of polyethers a).
• Suitable polyether monools a-ii) are polyether monools having a number average molecular weight of 1000 to 15,000, preferably 3000 to 12,000 and more preferably 6000 to 12,000.
• the polyether monools are prepared by the alkoxylation of monofunctional starting compounds with alkylene oxides, preferably ethylene oxide, propylene oxide or butylene oxide, more preferably propylene oxide. If ethylene oxide is used, it is used in an amount of up to 40% by weight, based on the weight of the polyether.
• the polyethers are preferably prepared either by the KOH process or by mixed metal cyanide catalysts. The latter process results in products with low a degree of unsaturation.
• the polyethers have a maximum total degree of unsaturation of less than 0.04 milliequivalents/g (meq/g) in some cases less than 0.02 meq/g, in other cases less than 0.01 meq/g and in some situations 0.007 meq/g or less.
• the amount of unsaturation will vary depending on the method used to prepare the polyether as well as the molecular weight of the polyerther.
• These polyether monools are known and can be produced by the methods set forth previously for preparing the polyether polyols, as a non-limiting example by the propoxylation of suitable starter molecules. In another non-limiting example, minor amounts (up to 20% by weight, based on the weight of the polyol) of ethylene oxide can also be used.
• ethylene oxide if ethylene oxide is used, it can be used as the initiator for or to cap the polypropylene oxide groups.
• starter molecules include aliphatic, cycloaliphatic and araliphatic alcohols, phenol and substituted phenols, such as methanol, ethanol, the isomeric propanols, butanols, pentanols and hexanols, cyclohexanol and higher molecular weight compounds such as nonylphenol, 2-ethylhexanol and a mixture of C 12 to C 15 , linear, primary alcohols (Neodol 25, available from Shell). Also suitable are unsaturated alcohols such as allyl alcohol; and hydroxy functional esters such as hydroxyethyl acetate and hydroxyethyl acrylate. Preferred are the higher molecular weight monohydroxy compounds, especially nonyl phenol and mixtures of C 12 to C 15 , linear, primary alcohols.
• polyethers a-ii) are present as the sole monofunctional component, they are preferably present in a minimum amount of 10% by weight, more preferably 20% by weight and most preferably 30% by weight, and a maximum amount of 80% by weight, preferably 70% by weight and more preferably 60% by weight. The preceding percentages are based on the total weight polyethers a).
• Suitable isocyanates b-i) include the known monomeric organic diisocyanates represented by the formula, R(NCO) 2 , in which R represents an organic group obtained by removing the isocyanate groups from an organic diisocyanate having a molecular weight of 112 to 1,000, preferably 140 to 400.
• Preferred diisocyanates are those represented by the above formula in which R represents a divalent aliphatic hydrocarbon group having from 4 to 18 carbon atoms, a divalent cycloaliphatic hydrocarbon group having from 5 to 15 carbon atoms, a divalent araliphatic hydrocarbon group having from 7 to 15 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 15 carbon atoms.
• suitable organic diisocyanates include 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate, 1-isocyanato-2-isocyanatomethyl cyclopentane, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (isophorone diisocyanate or IPDI), bis-(4-isocyanato-cyclohexyl)-methane, 1,3- and 1,4-bis-(isocyanatomethyl)-cyclohexane, bis-(4-isocyanatocyclo-hexyl)-methane, 2,4′-diisocyanato-dicyclohexyl methane, bis-(
• Monomeric polyisocyanates containing 3 or more isocyanate groups such as 4-isocyanatomethyl-1,8-octamethylene diisocyanate and aromatic polyisocyanates such as 4,4′,4′′-triphenylmethane triisocyanate and polyphenyl polymethylene polyisocyanates obtained by phosgenating aniline/formaldehyde condensates may also be used in an amount of up to 20% by weight, based on the weight of isocyanates b).
• polyisocyanate adducts prepared from the preceding monomeric polyisocyanates and containing isocyanurate, uretdione, biuret, urethane, allophanate, iminooxadiazine dione, carbodiimide and/or oxadiazinetrione groups.
• Preferred diisocyanates include bis-(4-isocyanatocyclohexyl)-methane, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, ⁇ , ⁇ , ⁇ ′, ⁇ ′-tetramethyl-1,3- and/or -1,4-xylylene diisocyanate, 2,4- and/or 2,6-toluylene diisocyanate, and 2,4- and/or 4,4′-diphenylmethane diisocyanate.
• Diisocyanates b-i) are present in a amount of up to 100% by weight.
• diisocyanates b-ii) are present in a minimum amount of 20% by weight, preferably 30% by weight and more preferably 40% by weight, and a maximum amount of 90% by weight, preferably 80% by weight and more preferably 70% by weight.
• the preceding percentages are based on the total weight of isocyanates b).
• Suitable isocyanates b-ii) include those corresponding to the formula R(NCO), wherein R is defined as previously set forth with regard to the organic diisocyanates.
• Suitable monoisocyanates include those corresponding to the diisocyanates previously set forth. Examples include butyl isocyanate, hexyl isocyanate, octyl isocyanate, 2-ethylhexyl isocyanate, stearyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate and benzyl isocyanate.
• monoisocyanates b-ii) When monoisocyanates b-ii) are present as the sole monofunctional component, they are preferably present in a minimum amount of 10% by weight, more preferably 20% by weight and most preferably 30% by weight, and a maximum amount of 80% by weight, preferably 70% by weight and more preferably 60% by weight. The preceding percentages are based on the total weight isocyanates b).
• Suitable compounds c) containing reactive silane groups are those corresponding to formula I
• X represents identical or different organic groups which are inert to isocyanate groups below 100° C., provided that at least two of these groups are alkoxy or acyloxy groups, preferably alkyl or alkoxy groups having 1 to 4 carbon atoms and more preferably alkoxy groups,
• Y represents a linear or branched alkylene group containing 1 to 8 carbon atoms, preferably a linear group containing 2 to 4 carbon atoms or a branched group containing 5 to 6 carbon atoms, more preferably a linear group containing 3 carbon atoms and
• R 1 represents an organic group which is inert to isocyanate groups at a temperature of 100° C. or less, provided that R 1 is not a succinate group, preferably an alkyl, cycloalkyl or aromatic group having 1 to 12 carbon atoms and more preferably an alkyl, cycloalkyl or aromatic group having 1 to 8 carbon atoms, or R 1 represents a group corresponding to formula II
• X represents methoxy, ethoxy groups or propoxy groups, more preferably methoxy or ethoxy groups
• Y is a linear group containing 3 carbon atoms.
• suitable aminoalkyl alkoxysilanes and aminoalkyl acyloxysilanes of formula I, which contain secondary amino groups include N-phenylaminopropyl-trimethoxysilane (available as A-9669 from OSI Corporation), bis-( ⁇ -trimethoxysilylpropyl)amine (available as A-1170 from OSI Corporation), N-cyclohexylaminopropyl-triethoxysilane, N-methylaminopropyl-trimethoxysilane, N-butylaminopropyl-trimethoxysilane, N-butylaminopropyl-triacyloxysilane, 3-(N-ethyl)amino-2-methylpropyl-trimethoxysilane, 4-(N-ethyl)amino-3,3-dimethylbutyl-trimethoxysilane and the corresponding alkyl diethoxy, alkyl dimethoxy and alkyl diacy
• a special group of compounds containing alkoxysilane groups, which correspond to formula I and are especially preferred for use as compounds c), are those containing aspartate groups and corresponding to formula III
• R 2 and R 5 are identical or different and represent organic groups which are inert to isocyanate groups at a temperature of 100° C. or less, preferably alkyl groups having 1 to 9 carbon atoms, more preferably alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl or butyl groups and
• R 3 and R 4 are identical or different and represent hydrogen or organic groups which are inert towards isocyanate groups at a temperature of 100° C. or less, preferably hydrogen.
• the compounds of formula III are prepared by reacting aminosilanes corresponding to formula IV
• suitable aminoalkyl alkoxysilanes and aminoalkyl acyloxysilanes corresponding to formula IV include 3-aminopropyl-triacyloxysilane, 3-aminopropyl-methyldimethoxysilane; 6-aminohexyl-tributoxysilane; 3-aminopropyl-trimethoxysilane; 3-aminopropyl-triethoxysilane; 3-aminopropyl-methyldiethoxysilane; 5-aminopentyl-trimethoxysilane; 5-aminopentyl-triethoxysilane; 4-amino-3,3-dimethyl-butyl-trimethoxysilane; and 3-aminopropyl-triisopropoxysilane. 3-amino-propyl-trimethoxysilane and 3-aminopropyl-triethoxysilane are particularly preferred.
• optionally substituted maleic or fumaric acid esters suitable for preparing the aspartate silanes include the dimethyl, diethyl, dibutyl (e.g., di-n-butyl), diamyl, di-2-ethylhexyl esters and mixed esters based on mixture of these and/or other alkyl groups of maleic acid and fumaric acid; and the corresponding maleic and fumaric acid esters substituted by methyl in the 2- and/or 3-position.
• the dimethyl, diethyl and dibutyl esters of maleic acid are preferred, while the diethyl esters are especially preferred.
• component c) The compounds corresponding to formula I are preferably used as component c). To obtain the benefits of the present invention, they should be present in an amount of at least 10% by weight, preferably at least 30% by weight, more preferably at least 50% by weight and most preferably at least 80% by weight.
• component c) may also contain aminosilanes that do not correspond to formula I, such as the primary aminosilanes corresponding to formula IV.
• compositions obtained by the process of the present invention may be cured in the presence of water or moisture to prepare coatings, adhesives or sealants.
• the compositions cure by “silane poly-condensation” from the hydrolysis of alkoxysilane groups to form Si—OH groups and their subsequent reaction with either Si—OH or Si—OR groups to form siloxane groups (Si—O—Si).
• Suitable acidic or basis catalysts may be used to promote the curing reaction.
• acids such as paratoluene sulfonic acid; metallic salts such as dibutyl tin dilaurate; tertiary amines such as triethylamine or triethylene diamine; and mixtures of these catalysts.
• metallic salts such as dibutyl tin dilaurate
• tertiary amines such as triethylamine or triethylene diamine
• mixtures of these catalysts and mixtures of these catalysts.
• the previously disclosed, low molecular weight, basic aminoalkyl trialkoxysilanes also accelerate hardening of the compounds according to the invention.
• the one-component compositions generally may be either solvent-free or contain up to 70%, preferably up to 60% organic solvents, based on the weight of the one-component composition, depending upon the particular application.
• Suitable organic solvents include those which are known from either from polyurethane chemistry or from coatings chemistry.
• compositions may also contain known additives, such as leveling agents, wetting agents, flow control agents, antiskinning agents, antifoaming agents, fillers (such as chalk, lime, flour, precipated and/or pyrogenic silica, aluminum silicates and high-boiling waxes), viscosity regulators, plasticizers, pigments, dyes, UV absorbers and stabilizers against thermal and oxidative degradation.
• additives such as leveling agents, wetting agents, flow control agents, antiskinning agents, antifoaming agents, fillers (such as chalk, lime, flour, precipated and/or pyrogenic silica, aluminum silicates and high-boiling waxes), viscosity regulators, plasticizers, pigments, dyes, UV absorbers and stabilizers against thermal and oxidative degradation.
• the one-component compositions may be used with any desired substrates, such as wood, plastics, leather, paper, textiles, glass, ceramics, plaster, masonry, metals and concrete. They may be applied by standard methods, such as spraying, spreading, flooding, casting, dipping, rolling and extrusion.
• the one-component compositions may be cured at ambient temperature or at elevated temperatures.
• the moisture-curable compositions are cured at ambient temperatures.
• Nonylphenol (183 g, 0.89 eq) was charged to a stainless-steel reactor.
• Zinc hexacyanocobaltate-tert-butyl alcohol complex (0.143 g, prepared as described in U.S. Pat. No. 5,482,908) was added and the mixture was heated with stirring under vacuum at 130° C. for one hour to remove traces of water from the nonylphenol starter.
• Propylene oxide (6407 g, 145.6 eq) was introduced into the reactor over 6 hours. After the epoxide addition was completed, the mixture was heated to 130° C. until no further pressure decrease occurred. The product was vacuum stripped and then drained from the reactor.
• the resulting polyether had an OH number of 8.5, an equivalent weight of 6612 and a functionality of 1.
• a 2 liter round bottom flask was fitted with agitator, nitrogen inlet, condenser, heater and addition funnel.
• Into the flask were charged 36.2 g (0.33 eq) of isophorone diisocyanate, 733.9 g (0.13 eq) of polyether diol 1, 264.5 g (0.04 eq) of polyether monool 2 and 0.23 g of dibutyltin dilaurate.
• 59.7 g (0.16 eq) of silane functional aspartate 1 were added and the flask was heated at 60° C.
• a 2 liter round bottom flask was fitted with agitator, nitrogen inlet, condenser, heater and addition funnel.
• Into the flask were charged 35.33 g (0.32 eq) of isophorone diisocyanate, 602.3 g (0.10 eq) of polyether diol 1, 400.5 g (0.06 eq) of polyether monool 2 and 0.22 g of dibutyltin dilaurate.
• 51.6 g (0.16 eq) of silane functional aspartate 1 were added and the flask was heated at 60° C.
• Example 2 was repeated with the exception that 34.55 g (0.31 eq) of isophorone diisocyanate, 502.0 g (0.087 eq) of polyether diol 1, 502.2 g (0.069 eq) of polyether monool 2 and 56.9 g (0.16 eq) of silane functional aspartate 1 were used.
• the resulting product had a viscosity of 39,000 mPa.s at 25° C.
• Example 2 was repeated with the exception that 95.1 g (0.43 eq) of isophorone diisocyanate, 1134 g (0.20 eq) of polyether diol 1, 1700.4 g (0.233 eq) of polyether monool 2 and 160.2 g (0.43 eq) of silane functional aspartate 1 were used.
• the resulting product had a viscosity of 27,700 mPa.s at 25° C.
• a 5 liter round bottom flask was fitted with agitator, nitrogen inlet, condenser, heater and addition funnel.
• Into the flask were charged 139.3 g (1.26 eq) of isophorone diisocyanate, 3643.3 g (0.63 eq) of polyether diol 1 and 0.8 g of dibutyltin dilaurate.
• 229.8 g (0.63 eq) of silane functional aspartate 1 were added and the flask was heated at 60° C. for an additional 1 hour until no NCO remained as determined by an IR spectrum.
• 20 g of vinyl trimethoxysilane were added as moisture scavenger.
• the resulting product had a viscosity of 73,000 mPa.s at 25° C.
• STP's prepared in situ were formulated into sealants using the following typical formulation and procedure.
• Comparison STP's 5 and 6 were formulated at a 70:30 ratio.
• the ingredients were mixed for one minute in length at a speed of 2200 rpm.
• a portion of the filler was added to the mixing container.
• the ingredients were mixed for one minute at a speed of 2200 rpm.
• the remaining filler was added to the mixing container.
• the ingredients were mixed for one minute in length at a speed of 2200 rpm.
• the side of the mix container was scraped and the ingredients were mixed for one additional minute at a speed of 2200 rpm to incorporate all of the filler into the mixture.
• the resulting product was degassed at 50° C. and under full vacuum (>28 mm Hg) for one hour. The material was used immediately.
• Exxon Jayflex DIDP was used as the plasticizer.
• An aminosilane (Silquest A-1120, available from OSI Corporation) was used as the adhesion promoter.
• a vinyltrimethoxysilane (Silquest A-171, available from OSI Corporation) was used as the desiccant.
• the filler used was Specialty Minerals Ultra P Flex precipitated calcium carbonate (mean particle size of 0.07 microns).
• the catalyst used was dibutyltin dilaurate.
• sealant formulations were cast onto 0.25 inch thick polyethylene sheets and cured at standard conditions of 20° C., 50% relative humidity for at least two weeks before testing.
• Tensile strength, percent elongation and 100% modulus were determined according to ASTM D-412. The results are set forth in the following table.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Polyurethanes Or Polyureas (AREA)
• Sealing Material Composition (AREA)
• Paints Or Removers (AREA)

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• 2003
  • 2003-10-22 US US10/690,953 patent/US6809170B2/en not_active Expired - Fee Related
• 2004
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